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View, Critique, and Give Advice Pertaining to My Thesis Work SYNTHESIS AND CHARACTERIZATION OF CONJUGATED MATERIALS WITH PHOSPHORUS By FENG LI LAUGHLIN Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Thesis Advisor: Dr. John D. Protasiewicz Department of Chemistry CASE WESTERN RESERVE UNIVERSITY January, 2013 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation of Feng Li Laughlin ______________________________________________________ Doctor of Philosophy candidate for the ________________________________degree *. Thomas G. Gray (signed)_______________________________________________ (chair of the committee) Malcolm E. Kenney ________________________________________________ Gregory P. Tochtrop ________________________________________________ Lei Zhu ________________________________________________ John D. Protasiewicz ________________________________________________ ________________________________________________ (date) _______________________ August 2012 *We also certify that written approval has been obtained for any proprietary material contained therein. Dedicated To: My family: Yingjie (mom), Patrick (husband), and Veronika (daughter) i Table of Contents Dedication……………………………………………………………………………………i Table of Contents……………………………………………………………………………ii List of Tables…………………………………………………………………………………iv List of Figures………………………………………………………………………………vi List of Schemes………………………………………………………………………………x List of Abbreviations………………………………………………………………………xi Acknowledgements…………………………………………………………………………xiv Abstract……………………………………………………………………………………xvi Chapter 1. General Introduction 1.1 π-Conjugated Materials ………………………………………………………………1 1.2 Conjugated Materials with Main Group Elements……………………………………3 1.3 Conjugated Materials with Phosphorus…………………………………………………7 1.4 Linear conjugated monomers and polymers with P=C Bonds………………………16 1.5 Benzoxaphospholes (BOPs)…………………………………………………………23 1.6 Proposed Work………………………………………………………………………25 1.7 Works Cited……………………………………………………………………………27 Chapter 2. Synthesis and Characterization of Benzobisoxaphospholes (BBOPs) 2.1 Introduction……………………………………………………………………………33 2.2 Results and Discussion………………………………………………………………42 2.3 Conclusions……………………………………………………………………………55 2.4 Experimental…………………………………………………………………………56 ii 2.5 Works Cited…… ……………………………………………………………………63 Chapter 3. Synthesis and Characterization of Naphthoxaphospholes (NOPs) 3.1 Introduction …………………………………………………………………………65 3.2 Results and Discussion ………………………………………………………………68 3.3 Conclusions …………………………………………………………………………86 3.4 Experimental …………………………………………………………………………88 3.5 Works Cited …………………………………………………………………………104 Chapter 4. Synthesis and Characterization of Naphthobisoxaphospholes (NBOPs) 4.1 Introduction ……………………………………………………………………106 4.2 Results and Discussion …………………………………………………………115 4.3 Conclusions ……………………………………………………………………134 4.4 Experimental ……………………………………………………………………136 4.5 Works Cited……………………………………………………………………146 Chapter 5. Conclusions…………………………………………………………………150 Appendix A. Crystal Structure Determination and Data……………………………………155 Appendix B. Selected 31P{1H}, 1H and 13C{1H} NMR Spectra …………………………217 Appendix C. Absorption and Emission Spectra ……………………………………………296 Bibliography………………………………………………………………………………319 iii List of Tables Table 1.1 Absorption data for conjugated oligomers and polymer with P=P bond -6 Table 2.1 Absorption and emission data for 2.19 (conc. 5 × 10 M in CH2Cl2, except 2.19d, in MeOH) -6 Table 2.2 Absorption and emission data for 2.20 (conc. 5 × 10 M in CH2Cl2) Table 2.3 31P{1H} NMR data of BBOPs and BOPs Table 2.4 13C{1H} NMR data of BBOPs and BOPs Table 2.5 Selected Bond lengths (Å) and bond angles (˚) for 2.28a and 2.9 -6 Table 2.6 Absorption and emission data for 2.28 (conc. 5 × 10 M in CH2Cl2) Table 2.7 Absorption and emission data for BOPs (MeOH) Table 2.8 Reduction potentials for 2.28 (V vs. SCE) Table 2.9 Reduction potentials for BOPs (V vs. SCE) Table 2.10 Reduction potentials for 2.20 (V vs. SCE) Table 2.11 Crystal data and collection parameters for 2.28a Table 3.1 31P{1H} NMR data for BOPs and NOPs Table 3.2 13C{1H} NMR data for BOPs and NOPs Table 3.3 Selected bond lengths (Å) and bond angles (˚) for 3.3b and 3.3d -6 Table 3.4 Absorption and emission data for NOPs (conc. 5 × 10 M in CH2Cl2) Table 3.5 Reduction potentials for 3.3a-d and 3.3g (V vs. SCE) Table 3.6 Crystal data and collection parameters for 3.12, 3.3b and 3.3d 31 1 Table 4.1 P{ H} NMR (CDCl3) data of R-NOPs and R2-NBOPs Table 4.2 31P{1H} NMR data of BOPs and BBOPs 13 1 Table 4.3 C{ H} NMR (CDCl3) data for C=P atoms of R2-NBOP compared to R-NOPs iv Table 4.4 Selected bond lengths (Å) and bond angles (˚) for compounds 4.5a and 4.5c Table 4.5 P=C bond lengths (Å) for some other oxaphosphole compounds Table 4.6 UV-vis and fluorescence of NOPs Table 4.7 UV-vis absorption λmax Table 4.8 Fluorescence emission data (nm) of NOPs and NBOPs Table 4.9 Reduction potentials Table 4.10 Crystal data and collection parameters of 4.4, 4.5a and 4.5c v List of Figures Figure 1.1 The molecular orbitals of 1,3-butadiene Figure 1.2 Examples of conjugated polymers Figure 1.3 Examples of conjugated polymers containing heteroatom Figure 1.4 Examples of multi-heterocyclic conjugated compounds Figure 1.5 Examples of donor-acceptor-donor (DAD) conjugated materials Figure 1.6 Compounds with Si=C bonds or Si=Si bonds Figure 1.7 Comparison of frontier orbitals for some E=E bonds (E = C, N, P) Figure 1.8 Structures of different types of conjugated moieties with phosphorus Figure 1.9 Examples of conjugated materials with arylphosphane moieties Figure 1.10 Conjugated materials containing phospholes Figure 1.11 Examples of stable compounds with P=E bonds (E = C, Si, P) Figure 1.12 Structures of building block: PPV vs. phospha-PPV Figure 1.13 The first polymer with P=C bonds and the corresponding model compounds Figure 1.14 Conjugated oligomers and polymers with P=P bonds Figure 1.15 Examples of linear conjugated polymers with phosphorus Figure 1.16 Structural diagram of 1.24a Figure 1.17 Torsional angle of 1.24a Figure 1.18 Structure of 2-substituted-1,3-benzoxaphospholes (R-BOPs) Figure 1.19 Design of the new π-conjugated materials with OPs Figure 1.20 Structure of target compounds BBOPs, NOPs and NBOPs Figure 2.1 Different isomers of benzobisoxaphospholes (BBOPs) Figure 2.2 Electronic delocalization vi Figure 2.3 Compounds 2.9 with torsion angle Figure 2.4 Compounds 2.10, Aryl-BBOPs t Figure 2.5 Compounds Bu2-BBOP and Ad2-BBOP Figure 2.6 Polymers with cis- and trans-p-benzobisoxazole building blocks Figure 2.7 Monomers with cis- and trans-p-benzobisoxazole building block and polymer Figure 2.8 Compounds 2.19 were prepared by Marlena P. Washington 1 Figure 2.9 Aryl substituted BBOP 2.20, prepared by Vittal B. Gudimetla 1 Figure 2.10 H NMR spectrum of 2.28a (CDCl3, 400 Hz) Figure 2.11 Compounds R2-BBOP with carbon position numbers Figure 2.12 Thermal ellipsoid diagrams structural representation of 2.28a Figure 2.13 UV-vis absorption spectrum and fluorescence emission of 2.28, emission excited -6 at 300 nm (conc. 5 × 10 M in CH2Cl2) Figure 2.14 Overlaid cyclic voltammograms for 2.28 Figure 2.15 Overlaid cyclic voltammograms for 2.20 Figure 3.1 Different isomers of naphthoxaphospholes (NOPs) Figure 3.2 Thermal ellipsoid diagrams of 3.12 Figure 3.3 Packing diagrams of 3.12 showing intermolecular hydrogen bonding Figure 3.4 Structure of 2-phosphino-naphthalene (3.14) and oxidized phosphine (3.13 ) Figure 3.5 MO diagram and SOMO for radical cation of 3.13 Figure 3.6 Thermal ellipsoid diagrams of 3.3b Figure 3.7 Thermal ellipsoid diagrams of 3.3d Figure 3.8 Packing diagram for compound 3.3d Figure 3.9 Absorption and emission spectra of NOPs: 3.3a, 3.3b (top), 3.3c-g (bottom) (conc. -6 5 × 10 M in CH2Cl2) vii Figure 3.10 Compounds 3.3a-g (0.1 M in CH2Cl2) under room light and UV light Figure 3.11 Cyclic voltammogram of 3.3a-d and 3.3g (conc. is 0.001 M in THF) Figure 3.12 MO diagrams for Ph-NOP and Ph-BOP Figure 3.13 MO diagrams for Ph-NOP and tBu-NOP Figure 3.14 Scan rate vs. Ep plot of ferrocene redox couple Figure 3.15 Scan rate vs. Ep plot of the redox couple of compound 3.3c Figure 3.16 Variable scan rate voltammogram for compound 3.3c (scan rates of 25 to 200 mV/s, conc. is 0.001 M in THF) Figure 4.1 Different isomers of naphthobisoxaphospholes (NBOPs) Figure 4.2 Isomers of S-type of NBOP Figure 4.3 Structure of S-type heterocyclic compounds Figure 4.4 Naphthodithiophenes (NDTs) with S- and U-type structures Figure 4.5 S-type of naphthodithiophenes (NDTs) 4.21 and 4.22 Figure 4.6 S-type of naphthodithiophenes (NDTs) 4.23 Figure 4.7 S-type naphthodifuran (NDF) 4.24 Figure 4.8 S-type naphthodifuran (NDF) 4.25 Figure 4.9 Dicyclopentanaphthalene (4.26), analogue of NDF Figure 4.10 Naphtho[1,2-d:5,6-d’]bisoxazoles and Naphtho[2,1-d:6,5-d’]bisoxazoles Figure 4.11 Structure of phosphate, phosphonate and primary phosphine Figure 4.12 1H NMR spectrum of 4.5a Figure 4.13 Structure of R2-NBOP with carbon position numbers Figure 4.14 Structure and stability of 2.28a, 3.3a and 4.5a viii 31 1 t Figure 4.15 Time-dependent P{ H} NMR spectra of Bu-BBOP (2.28a) in CDCl3 open to air 31 1 t Figure 4.16 Time-dependent P{ H} NMR spectra of Bu-NOP (3.3a) in CDCl3 open to air 31 1 t Figure 4.17 Time-dependent P{ H} NMR spectra of Bu2-NBOP (4.5a) in CDCl3 open to air Figure 4.18 Thermal ellipsoid diagram of 2,6-diphosphino-1,5-naphthylenediol (4.4) Figure 4.19 Packing diagram for 4.4 Figure 4.20 Thermal ellipsoid diagram of 2,7-di-tert-butyl-naphtho[1,2-d:5,6- d’]bisoxaphosphole (4.5a) Figure 4.21 Thermal ellipsoid diagram of 2,7-di-phenyl-naphtho[1,2-d:5,6- d’]bisoxaphosphole (4.5c) Figure 4.22 Packing diagram for compound 4.5a Figure 4.23 Packing diagram for compound 4.5c Figure 4.24 UV-vis absorption spectra of R2-NBOPs (4.5a-c) Figure 4.25 Solution of 4.16c (0.5 M in CH2Cl2) under room light and UV light (λF,max = 422 nm) Figure 4.26 Fluorescence emission spectra of NBOPs (4.5a-c) Figure 4.27 Overlaid cyclic voltammograms for 4.5a and 4.5c Figure 4.28 Scan rate vs.
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